Silicone compositions for personal care products and method for making

ABSTRACT

A composition and method for making a silicone composition is provided which comprises at least one polysiloxane or silicone resin, at least one linker, and at least one molecular hook wherein the molecular hook comprises a heterocyclic trimethylpyrimidinium compound.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of application Ser. No. 09/616,532,filed Jul. 14, 2000, now U.S. Pat. No. 6,488,921 which is herebyincorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

The present invention relates to compositions for personal careproducts. More particularly, the present invention relates to siliconecompositions which achieve conditioning benefits in hair care products.

Silicones are widely used in hair care products due to the conditioningbenefit that they impart to hair. By modem day technology, the siliconeis deposited on hair during the application process but is held only byweak physical forces, such as hydrogen bonding or van der Waalsinteractions. Generally, conditioning benefits are attributed to thedeposition of high molecular weight, high viscosity fluids and gumswhich can weigh down the hair. Because the interactive forces are weak,the benefits of silicone by deposition are short lived. Beneficialconditioning effects can also be caused by treating hair with silanolcapped amino-functionalized silicones. These can undergo condensationcure reactions on hair to form somewhat durable films.

It is widely known by those skilled in the art that covalent bonding isone key to “permanent” hair treatment. Processes which alter thestructure of the hair, such as permanent wave and color treatmentmethods, do provide longer lasting effects. These processes includeglycolate reduction and peroxide reoxidation. A significant disadvantageof these processes is that they are very damaging to hair and can onlybe carried out infrequently.

Gough et al. in U.S. Pat. Nos. 5,523,080 and 5,525,332 describe thesynthesis of silicone-azlactone polymers which exhibit covalent bondingand “permanent” conditioning benefit. Gough et al. discuss incorporatingan azlactone-functionalized copolymer which consists of vinylazlactoneand methacryloyl polydimethylsiloxane monomers into a silicone-activegroup-hair structure. The hair treatment using the silicone-azlactonepolymers does not consist of the steps of reduction with a glycolate orreoxidation with peroxide.

It is desirable to produce silicone compositions which can be used totreat damaged hair and provide durable benefits. Thus, silicone productsare constantly being sought which can both covalently bond to hair aswell as impart hair care benefits appreciated by consumers.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a silicone composition which comprises atleast one polysiloxane or silicone resin, at least one linker, and atleast one molecular hook wherein the molecular hook comprises aheterocyclic trimethylpyrimidinium compound.

The present invention further provides a method for making a siliconecomposition comprising at least one polysiloxane or silicone resin, atleast one linker, and at least one molecular hook. The method comprisescombining a linker, a molecular hook, and a polysiloxane or siliconeresin wherein the molecular hook comprises a heterocyclictrimethylpyrimidinium compound.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a silicone composition which includes atleast one polysiloxane or silicone resin, at least one linker, and atleast one molecular hook. The linker is bound to both a molecular hookand to an atom of a polysiloxane or silicone resin. Preferably thelinker is bound to a polysiloxane or silicone resin through a silicon(Si), carbon (C), oxygen (O), nitrogen (N), or sulfur (S) atom, and mostpreferably through a silicon atom. When more than one linker is present,it is also contemplated that linkers may be bound to a polysiloxane orsilicone resin through more than one type of atom, for example throughboth silicon and carbon atoms.

The present invention includes a silicone composition having theformula:

M_(a)M′_(b)D_(c)D′_(d)T_(e)T′_(f)Q_(g)

where the subscripts a, b, c, d, e, f and g are zero or a positiveinteger, subject to the limitation that the sum of the subscripts b, dand f is one or greater; where M has the formula:

R⁴⁰ ₃SiO_(1/2),

M′ has the formula:

(Z—Y)R⁴¹ ₂SiO_(1/2),

D has the formula:

R⁴² ₂SiO_(2/2),

D′ has the formula:

(Z—Y)R⁴³SiO_(2/2),

T has the formula:

R⁴⁴SiO_(3/2),

T′ has the formula:

(Z—Y)SiO_(3/2),

and Q has the formula SiO_(4/2), where each R⁴⁰, R⁴¹, R⁴², R⁴³, R⁴⁴ isindependently at each occurrence a hydrogen atom, C₁₋₂₂ alkyl, C₁₋₂₂alkoxy, C₁₋₂₂ alkenyl, C₆₋₁₄ aryl, C₆₋₂₂ alkyl-substituted aryl, orC₆₋₂₂ aralkyl which groups may be halogenated, for example, fluorinatedto contain fluorocarbons such as C₁₋₂₂ fluoroalkyl, or may contain aminogroups to form aminoalkyls, for example aminopropyl oraminoethylaminopropyl, or may contain polyether units of the formula(CH₂CHR⁴⁵O)_(k) where R⁴⁵ is CH₃ or H and k is in a range between about4 and 20; Z, independently at each occurrence, represents a molecularhook; and Y, independently at each occurrence, represents a linker. Theterm “alkyl” as used in various embodiments of the present invention isintended to designate both normal alkyl, branched alkyl, aralkyl, andcycloalkyl radicals. Normal and branched alkyl radicals are preferablythose containing in a range between about 1 and about 12 carbon atoms,and include as illustrative non-limiting examples methyl, ethyl, propyl,isopropyl, butyl, tertiary-butyl, pentyl, neopentyl, and hexyl.Cycloalkyl radicals represented are preferably those containing in arange between about 4 and about 12 ring carbon atoms. Some illustrativenon-limiting examples of these cycloalkyl radicals include cyclobutyl,cyclopentyl, cyclohexyl, methylcyclohexyl, and cycloheptyl. Preferredaralkyl radicals are those containing in a range between about 7 andabout 14 carbon atoms; these include, but are not limited to, benzyl,phenylbutyl, phenylpropyl, and phenylethyl. Aryl radicals used in thevarious embodiments of the present invention are preferably thosecontaining in a range between about 6 and about 14 ring carbon atoms.Some illustrative non-limiting examples of these aryl radicals includephenyl, biphenyl. and naphthyl. An illustrative non-limiting example ofa halogenated moiety suitable is trifluoropropyl.

The polysiloxanes or silicone resins of the present invention aretypically prepared by the hydrosilylation of an organohydrogen siliconehaving the formula:

M_(a)M^(H) _(b)D_(c)D^(H) _(d)T_(e)T^(H) _(f)Q_(g)

where the subscripts a, b, c, d, e, f and g are zero or a positiveinteger, subject to the limitation that the sum of the subscripts b, dand f is one or greater; M, D, T and Q are defined as above;

M^(H) has the formula:

R⁴¹ _(3-h)H_(h)SiO_(1/2),

D^(H) has the formula:

 H_(2-i)R⁴³ _(i)SiO_(2/2),

T^(H) has the formula:

HSiO_(3/2),

where each R⁴¹ and R⁴³ is independently as defined above; subscript h isin a range between 1 and 3; and subscript i is 0 or 1.

Hydrosilylation is typically accomplished in the presence of a suitablehydrosilylation catalyst. The catalysts preferred for use with thesecompositions are described in U.S. Pat. Nos. 3,715,334; 3,775,452; and3,814,730 to Karstedt. Additional background concerning the art may befound at J. L. Spier, “Homogeneous Catalysis of Hydrosilation byTransition Metals, in Advances in Organometallic Chemistry, volume 17,pages 407 through 447, F. G. A. Stone and R. West editors, published bythe Academic Press (New York, 1979). A preferred catalyst containsplatinum. Persons skilled in the art can easily determine an effectiveamount of platinum catalyst. Generally, an effective amount is in arange between about 0.1 parts per million and about 50 parts per millionof the total silicone composition composition.

The organohydrogen silicone compounds that are the precursors to thecompounds of the present invention may be prepared by the processdisclosed in U.S. Pat. No. 5,420,221. The '221 patent discloses theredistribution of polydimethylsiloxane polymers with organohydrogensilicone polymers and optionally, added chain stopper, to provide asilicone with randomly-distributed hydride groups using a Lewis acidcatalyst, preferably a phosphonitrilic compound.

Synthesis of the polysiloxane or silicone resin may also be performed byother method known to those skilled in the art, for example, thehydrosilylation of a monomer such as methyldichlorosilane could befollowed by co-hydrolysis with the appropriate dialkyldichlorosilane andoptionally, chlorotrimethylsilane.

It is to be noted that as pure compounds, the subscripts describing theorganohydrogen siloxane precursor and the hydrosilylation adduct of thepresent invention are integers as required by the rules of chemicalstoichiometry. The subscripts will assume non-integral values formixtures of compounds that are described by these formulas. Therestrictions on the subscripts heretofore described for thestoichiometric subscripts of these compounds are for the pure compounds,not the mixtures.

In specific embodiments of the present invention, the siliconecomposition typically comprises at least one compound of the followingformulas, (I), (II), (III), (IV), (V), (VI), or (VII):

 (R³⁷ ₃SiO_(1/2))_(a)[(Z—Y)R³⁸ ₂SiO_(1/2)]_(b)(SiO_(4/2))_(g)  (VII)

where each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸,R²⁹, R³⁰, R³¹, R³², R³³, R³⁴, R³⁵, R³⁶, R³⁷, and R³⁸ is independently ateach occurrence a hydrogen atom, C₁₋₂₂ alkyl, C₁₋₂₂ alkoxy, C₂₋₂₂alkenyl, C₆₋₁₄ aryl, and C₆₋₂₂ alkyl-substituted aryl, or C₆₋₂₂ aralkylwhich groups may be halogenated, for example, fluorinated to containfluorocarbons such as C₁₋₂₂ fluoroalkyl, may contain amino groups toform aminoalkyls, or may contain polyether units; Z, Z¹-Z¹⁰,independently at each occurrence, represents a molecular hook; and Y,Y¹-Y¹⁰, independently at each occurrence, represents a linker; wherein“m” in each formula has a value in a range between about 0 and about13,000, preferably about 0 and about 1000, more preferably between about1 and about 250, still more preferably between about 5 and about 250,even more preferably between about 10 and about 150, and most preferablybetween about 20 and about 120; “n” in each formula has a value in arange between about 0 and about 13,000, more preferably between about 0and about 50, more preferably between about 1 and about 20, still morepreferably between about 2 and about 10, and most preferably betweenabout 2 and about 5 with the proviso that in formula (II) “n” is not 0;“m+n” in each formula has a value in a range between about 1 and about26,000, preferably in a range between about 3 and about 250, and morepreferably between about 5 to about 150; “q” has a value of at least oneand “p+q” has a value of at least 3, preferably in a range between about3 and about 20, more preferably in a range between about 3 and about 10,and most preferably in a range between about 3 and 6. R¹⁻³⁸ ispreferably methyl. The preferred silicone composition includes acompound of the formula (I) or (II). The polysiloxane or silicone resintypically has a molecular weight in a range between about 100 and about6,000,000, preferably in a range between about 250 and about 50,000,more preferably in a range between about 500 and about 25,000, and mostpreferably in a range between about 500 and about 15,000.

The number of Y-Z moieties on a polysiloxane or silicone resin in thecomposition is at least one. In preferred embodiments the average numberof Y-Z moieties on a polysiloxane or silicone resin is in a rangebetween about 1 and about 100, more preferably in a range between about1 and about 20, still more preferably in a range between about 1 andabout 10.

In one embodiment of the present invention a polysiloxane- or siliconeresin-containing composition includes a preponderance of a specificlinear, branched, cross-linked, or cyclic polysiloxane or siliconeresin. In other embodiments of the present invention, a polysiloxane- orsilicone resin-containing composition comprises a mixture ofpolysiloxanes, mixture of silicone resins, or mixtures of polysiloxanesand silicone resins which may include linear, branched, cross-linked,and cyclic species. Also, suitable compositions may comprise one or morepolysiloxanes, silicone resins, and mixtures thereof which may containadventitious amounts of other species, for example, arising during thesynthesis process for said polysiloxanes or silicone resins, for exampleat a level in a range between about 0.0001 wt. % and about 5 wt. % basedon total silicon-containing species. In illustrative examples, suitablecompositions may contain adventitious amounts of D₄, or speciescontaining Si—H, Si—OH, Si—O-alkyl bonds, and mixtures thereof.

The molecular hook is a heterocyclic trimethylpyrimidinium compound ofthe formula (VIII):

wherein Y represents a linker and Q⁻ represents a counterion.

The counterion, Q⁻, can include halides, borates, phosphates, tosylates,mesylates, triflates, and other counterions known to those skilled inthe art. Q⁻ is preferably iodide, chloride, or bromide.

The linker comprises any C₁-C₁₀₀ alkyl, aryl, or alkylaryl group wherethe C₁₋₁₀₀ group can be interrupted by or substituted with aromaticgroups or aromatic-containing groups. The C₁₋₁₀₀ group may also containone or more heteroatoms such as O, N, or S. Furthermore, the C₁₋₁₀₀group may be unsubstituted or substituted with heteroatoms such ashalogen. Typically, the linker has the formulas (IX) through (XV):

where

r is in a range between about 1 and about 10, preferably 2 or 3;

s is in a range between about 0 and about 100, preferably 4 to 20;

t is in a range between about 0 and about 100, preferably in a rangebetween about 0 and about 20, and most preferably 0;

u is in a range between about 1 and about 10, preferably 1;

v is in a range between about 1 and about 10, preferably 2 or 3;

w is 1 or 2;

x is 1 or 2;

X is O, NOH, NOR, or NR, preferably O;

wherein R is independently at each occurrence hydrogen (H), C₁₋₂₂ alkyl,C₁₋₂₂ alkoxy, C₂₋₂₂ alkenyl, C₆₋₁₄ aryl, or C₆₋₂₂ alkyl-substitutedaryl, and C₆₋₂₂ aralkyl where the C can be unsubstituted or substitutedwith heteroatoms such as oxygen (O), nitrogen (N), sulfur (S) orhalogen;

wherein R³⁹ is independently at each occurrence hydrogen (H), C₁₋₂₂alkyl, C₁₋₂₂ alkoxy, C₂₋₂₂ alkenyl, C₆₋₁₄ aryl, C₆₋₂₂ alkyl-substitutedaryl, C₆₋₂₂ aralkyl, or fused ring system which may or may not be fusedto the phenyl group where the C can be unsubstituted or substituted withheteroatoms such as O, N, S or halogen. R³⁹ is preferably H. If R³⁹represents an aryl group, it can be fused to the ring in Formulas (XII)through (XV);

A is O, NOH, NOR, NR or S, preferably O;

B is O, NOH, NOR, NR or S, preferably O or NR and most preferably O;

and where the polysiloxane or the silicone resin is bound to the(CR₂)_(r)(Formula IX, X, XII, and XIII), (CR₂)_(v) (Formula XI and XIV),or (CR₂)_(w)(Formula XV). Any of the linker structures shown in Formulas(IX) through (XV) can also be interrupted with cycloaliphatic rings oraromatic rings. Substituents on the phenyl group of formulas (XII),(XIII), (XIV), and (XV) may be present at any free valence site. Thepolysiloxane or silicone resin may or may not contain otherfunctionalities by substitution at silicon atoms either the same as ordistinct from those bound to the linking groups described above, such asamine-, polyether-, alkyl-, or heteroalkyl-containing groups.

The linker is typically derived from a polysiloxane or silicone resinbound linker precursor which comprises a linker bound to a leavinggroup. Illustrative leaving groups include halides such as chloride,bromide and iodide; tosylate, mesylate, phosphate; cyclic leaving groups(that is, those in which the leaving group remains bound in the linker)such as epoxy or other cyclic leaving group containing at least oneheteroatom; and other leaving groups known to those skilled in the art.Preferred leaving groups are bromide, chloride, and iodide. Insynthesis, the leaving group is replaced by a molecular hook, so thatthe linker becomes bound to a molecular hook.

The method for making the silicone compositions of the present inventionincludes combining a molecular hook, a polysiloxane or silicone resin,and a linker. The sequence of addition can be varied, for example, thelinker and the molecular hook can be combined and this combination canbe sequentially combined with a polysiloxane or a silicone resin.Preferably, the linker is combined with a polysiloxane or silicone resinand the combination is sequentially combined with the molecular hook.

Silicone compositions of the present invention which include at leastone polysiloxane or silicone resin, at least one linker, and at leastone molecular hook typically impart cosmetic and other durable benefitsin products such as hair care products, but also including, textile careproducts, cosmetic products, oral care products, and animal careproducts. A particular advantage of the present invention is that manyof the described linkers provide solubility, in consumer relevant media,to the silicone composition as well as the potential for additional haircare benefits which may or may not be typically associated with thefunctional groups of the linker. In particular, the molecular hook ofthe present invention is thermally and hydrolytically stable.

In hair care applications, the silicone compositions can be delivered tothe hair in any appropriate formulation, for example, water or water andalcohol mixtures which can contain in a range between about 1% by weightand about 99% by weight alcohol based on the total formulation.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation.

In the following examples, D^(R1) through D^(R4) are defined as:

EXAMPLE 1

Silicone hydride fluid (MD₄₈D^(H) ₃M). A 1000 milliliter three-neckround bottom flask equipped with a mechanical stirrer, thermometerattached to a temperature controlling device and a drying tube wascharged with a silanol-terminated polydimethylsiloxane polymer (535.1grams, 7.23 moles dimethylsiloxy groups), a silicone hydride fluid(MD^(H) _(x)M, 30.35 grams=0.48 moles methylhydridosiloxy groups+0.019moles trimethylsiloxy groups), hexamethyldisiloxane (24.41 grams, 0.3moles trimethylsiloxy groups) and a linear phosphonitrilo catalyst (2.95grams of a 2% solution in silicone fluid, 100 parts per million). Themixture was stirred at 90° C. for two hours after which it was cooledand treated with magnesium oxide (1 gram, 0.0256 moles). The mixture wasfiltered through Celite to furnish the product as a clear, colorlessfluid with viscosity of 58.8 centistokes and hydride level of 828 partsper million. ¹H NMR (acetone-d₆): δ 4.74 (s, 3.0H, SiH), 0.12 (m,315.0H, SiCH₃).

EXAMPLE 2

Benzylchloride-substituted silicone polymer (MD₄₈D^(R1) ₃M). A 5 literthree-neck round bottom flask equipped with a stirbar, thermometerattached to a temperature controlling device, addition funnel and acondenser with a drying tube was charged with the silicone hydridepolymer (MD₄₈D^(H) ₃M, 931.2 grams, 0.77 moles hydride), 4-vinylbenzylchloride (7.56 grams, 0.050 moles), di-t-butylphenol (0.52 grams) andKarstedt's catalyst (95.3 mg of a 10% Pt solution of GE SiliconesProduct M^(Vi)M^(Vi) as solvent). The mixture was heated to 60° C. andadditional 4-vinylbenzyl chloride (110.16 grams, 0.72 moles) was addedover 60 minutes with a slight exotherm to 80° C. The reaction wasfollowed by gasiometric hydride analysis and was finished within 6 hoursafter the addition was complete. The reaction mixture was heated at 130°C. under vacuum to remove unreacted volatile compounds to provide aproduct with viscosity of 124 centistokes. ¹H NMR (acetone-d₆): δ7.33(m, 6.0H, phenyl), 7.22 (m, 6.0H, phenyl), 4.66 (s, 6.0H, CH₂Cl), 2.73(m, 6.0H, SiCH₂CH₂Ar), 2.24 (m, 3.0H, SiCH(CH₃)Ar), 1.39 (m, 9.0H,SiCH(CH₃)Ar), 0.93 (m, 6.0H, SiCH₂CH₂Ar), 0.12 (m, 315H, SiCH₃).

EXAMPLE 3

Hydroxypropyl-substituted silicone (MD₄₅D^(R2) _(3.5)M). A 2000milliliter three-neck round bottom flask equipped with a stirbar,thermometer attached to a temperature controlling device, additionfunnel, and a condenser with a drying tube was charged with allylalcohol (76.0 milliliters, 64.90 grams, 1.12 moles), 2-propanol (160grams), and Karstedt's catalyst (706.8 milligrams of a 1% Pt solution in2-propanol, 11 parts per million Pt). The solution was heated to 85° C.,and silicone hydride polymer MD₄₅D^(H) _(3.5)M (600 grams, 0.557 moleshydride) was added over 120 minutes. The reaction was followed bygasiometric hydride analysis and was finished within 6 hours after theaddition was complete. The 2-propanol was removed at 90° C. in vacuo toprovide a light tan silicone polyether fluid with viscosity of 170centistokes. ¹H NMR (acetone-d₆): δ 3.50 (t, 7.0H, SiCH₂CH₂CH₂OH), 1.60(m, 7.0H, SiCH₂CH₂CH₂O), 0.58 (m, 7.0H, SiCH₂CH₂CH₂O), 0.12 (m, 298.5H,SiCH₃).

EXAMPLE 4

Silicone with bromo-acetylated propyl substituents (MD₄₅D^(R3) _(3.5)M).A 500 milliliter three-neck round bottom flask equipped with a stirbar,thermometer attached to a temperature controlling device, Dean-Starktrap with a condenser and a drying tube was charged with bromoaceticacid (35.42 grams, 0.255 moles), Isopar C (Exxon Product, 280 grams),and the silicone hydroxypropyl fluid MD₄₅D^(R2) _(3.5)M (300.0 grams,0.268 equivalents hydroxy groups). The reaction mixture was sparged withnitrogen for 30 minutes at ambient temperature to remove the dissolvedair. para-Toluenesulfonic acid (2.50 grams, 13.1 millimoles) was addedand the reaction mixture was heated to 100° C. Water and Isopar C werecollected in the Dean-Stark trap. After two hours, the theoreticalamount of water was obtained (4.1 grams), and the reaction mixture wascooled to ambient conditions. Excess sodium carbonate was added toneutralize the reaction, and the salts were removed by filtrationthrough Celite after at least two hours of stirring. The volatilematerials were removed under vacuum to give 324.2 grams of product (98%yield). ¹H NMR (acetone-d₆): δ4.12 (t, 7.0H, CH₂CH₂OC(O)), 3.99 (s,7.0H, CH₂Br), 1.76 (m, 7.0H, SiCH₂CH₂CH₂O), 0.63 (m, 7.0H,SiCH₂CH₂CH₂O), 0.12 (m, 298.5H, SiCH₃).

EXAMPLE 5

Polyether-substituted silicone polymer (MD_(52.7)D^(R4) _(3.3)M). A 1000milliliter three-neck round bottom flask equipped with a stirbar,thermometer attached to a temperature controlling device, additionfunnel and a condenser with a drying tube was charged with anallyl-started poly(oxyethylene) (176.47 grams, 0.329 moles), 2-propanol(119.0 grams) and Karstedt's catalyst (86.6 milligrams of a 10% Ptsolution with GE Silicones Product M^(Vi)M^(Vi) as solvent). Thesolution was heated to 88° C., and the silicone hydride polymerMD_(52.7)D^(H) _(3.3)M (300.0 grams, 0.2917 moles hydride, prepared bythe same method as described above) was added over 90 minutes. Thereaction was followed by gasiometric hydride analysis and was finishedwithin 4 hours after the addition was complete. The volatile materialsincluding 2-propanol were removed at 90° C. under vacuum to provide alight tan silicone polyether fluid with viscosity of 1336 centistokes.¹H NMR (acetone-d₆): δ3.85 (m, 6.6H, CH₂CH₂OH), 3.74 (m, 6.6H,CH₂CH₂OH), 3.57 (s, 132.7H, OCH₂CH₂O), 341 (m, 6.6H, SiCH₂CH₂CH₂O), 1.63(m, 6.6H, SiCH₂CH₂CH₂O), 0.58 (m, 6.6H, SiCH₂CH₂CH₂O), 0.12 (m, 344.1H,SiCH₃).

EXAMPLE 6

Silicone polymer with bromo-acetylated polyether substituents(MD_(52.7)D^(R5) _(3.3)M). A 1000 milliliter three-neck round bottomflask equipped with a stirbar, thermometer attached to a temperaturecontrolling device and a Dean-Stark trap with a condenser and a dryingtube was charged with bromoacetic acid (34.00 grams, 0.245 moles),Isopar C (Exxon Product, 314 grams) and the polyether-substitutedsilicone MD_(52.7)D^(R4) _(3.3)M (397.50 grams, 0.257 equivalentshydroxy groups). The reaction mixture was sparged with nitrogen for 20minutes at ambient temperature to remove the dissolved air.para-Toluenesulfonic acid (2.36 grams, 13.7 millimoles) was added, andthe reaction mixture was heated to 100° C. Water and Isopar C werecollected in the Dean-Stark trap. After two hours, 98% of thetheoretical amount of water was obtained (4.4 grams), and the reactionmixture was cooled to ambient conditions. Potassium carbonate (3.80grams, 27.6 millimoles) was added to neutralize the reaction, and thesalts were removed by filtration through Celite after at least two hoursof stirring to provide product with viscosity of 1843 centistokes. ¹HNMR (acetone-d₆): δ 4.27 (m, 6.6H, CH₂CH₂OC(O)), 4.04 (s, 6.6H, CH₂Br),3.70 (m, 6.6H, OCH₂CH₂OC(O)), 3.58 (s, 132.7H, OCH₂CH₂O), 3.41 (m, 6.6H,SiCH₂CH₂CH₂O), 1.63 (m, 6.6H, SiCH₂CH₂CH₂O), 0.58 (m, 6.6H,SiCH₂CH₂CH₂O), 0.12 (m, 344.1H, SiCH₃).

EXAMPLE 7

Trimethylpyrimidinium-substituted silicone polymer (MD₄₈D^(R6) ₃M). To a500 milliliter round bottom flask containing a stir bar was added 151.2grams (36.543 millimoles) of the benzylchloride-substituted siliconepolymer MD₄₅D^(R1) ₃M. Sodium iodide (15.30 grams, 102.1 millimoles) wasadded as a solid with 200 milliliters of acetone. This mixture wasallowed to stir while 15.69 grams (101.7 millimoles) of1,4,6-trimethylpyrimidine-2-thione were added in portions as a solid. Anadditional 300 milliliters of acetone was then added to the pale yellowreaction mixture which was allowed to stir for 24 hours at roomtemperature. After this time, the reaction mixture was vacuum filteredto remove solids. The volatile materials were removed from the filtrateunder vacuum. The final product was isolated in 98.7% yield (163.2grams) as a clear, light yellow, rubbery solid. ¹H NMR (acetone-d₆): δ7.91 (s, 3.0 H, pyH), 7.47 (m, 6.0 H, phenyl), 7.21 (m, 6.0 H, phenyl),4.73 (s, 6.0 H, CH₂S), 4.14 (s, 9.0 H, NCH₃), 2.95 (s, 9.0 H,6-arylCH₃), 2.75 (s, 9.0 H, 4-arylCH₃), 2.71 (m, 6.0 H, SiCH₂CH₂), 2.22(m, 3.0 H, SiCH(CH₃)), 1.39 (d, 9.0 H, SiCH(CH₃)), 0.93 (m, 9.0 H,SiCH₂CH₂Ar), 0.12 (s, 315 H, SiCH₃).

EXAMPLE 8

Trimethylpyrimidinium-substituted silicone polymer (MD₄₅D^(R7) _(3.5)M).A flask was charged with 35.0 grams (8.0 millimoles) of the siliconepolymer MD₄₅D^(R3) _(3.5)M followed by 50 milliliters of acetone.Following the addition of 3.54 grams of1,4,6-trimethyl-pyrimidine-2-thione (22.7 millimoles), the suspensionwas left stirring for six hours, whereupon starting material stillremained by ¹H NMR. After the addition of four mole percent additionalthione, the mixture was left stirring overnight. The following morning,the mixture was centrifuged to remove the solid salts remaining, and theproduct solution was decanted and concentrated, affording 37.8 grams(87% yield) of polymer product. ¹H NMR (acetone-d₆): δ 8.03 (m, 3.5H,pyH), 4.39 (s, 7.0H, CH₂S), 4.26 (m, 10.5H, NCH₃, 4.14 (t, 7.0H,CH₂CH₂CH₂OC(O)), 3.02 (s, 7.0H, pyCH₃), 2.67 (s, 7.0H, pyCH₃), 1.78 (m,7.0H, CH₂CH₂CH₂OC(O)), 0.63 (t, 7.0H, CH₂CH₂CH₂OC(O)), 0.12 (m, 297H,SiMe).

EXAMPLE 9

Trimethylpyrimidinium-substituted polyether silicone polymer (MD₅₃D^(R8)_(3.3)M). A flask was charged with 33.5 grams (5.53 millimoles) of thesilicone polymer MD₅₃D^(R5) _(3.3)M. Acetone (50 milliliters) was addedfollowed by 2.90 grams of 1,4,6-trimethyl-pyrimidine-2-thione (22.7millimoles). The suspension was allowed to stir for 1.5 hours, afterwhich 0.08 mole percent of excess thione remained by ¹H NMRspectroscopy. After the addition of 1.97 grams (0.325 millimoles) moresilicone polymer, the mixture was left stirring overnight. The mixturewas then centrifuged to remove the solid salts remaining, and theproduct solution was decanted. The volatile materials were removed undervacuum affording 32.6 grams (86% yield) of polymer product. ¹H NMR(acetone-d₆): δ 7.96 (m, 3.5 H, pyH), 4.38 (s, 7.0 H, CH₂S), 4.26 (m,17.5H, NCH₃, OCH₂CH₂OC(O)), 3.70 (m, 7 H, CH₂OCH₂CH₂OC(O)), 3.58 (m,142.81H, OCH₂CH₂O), 3.39 (t, 7.0 H, SiCH₂CH₂CH₂O), 3.00 (s, 7H, pyCH₃),2.68 (s, 7H, pyCH₃), 1.62 (m, 7.0 H, SiCH₂CH₂CH₂O), 0.58 (m, 7.0 H,SiCH₂CH₂CH₂O), 0.12 (s, 344 H, SiCH₃).

It should be noted that while most reactions in which cationic polymerswere made were performed at room temperature, in most instances they canbe heated to speed the reaction.

EXAMPLE 10-11

Using the same procedures as described above for the structurallyanalogous polymers, the following materials were also synthesized:

MD₉₉D^(R6) ₃M

M^(R6)D₄₈M^(R6)

Silicone deposition. Polymers described in this invention impart durablebenefits to hair such as good combability, manageability, etc. Thedegree to which the new silicone materials interact with hair durably,after repeated shampooing, was measured. Hair switches were treated,extracted and shampooed 20 times with a commercially available shampoo(Prell®) and were then analyzed for silicon by x-ray fluorescence (XRF).The counts were converted to parts per million silicon deposition usingstandard methods.

TABLE 1 XRF data collected on hair switches treated with new siliconepolymers after extraction and 20 shampoos with Prell ®. TreatmentSilicone Solvent Time Deposition Switches Polymer (EtOH/water) pH (min)(ppm)¹ 1-3 MD₄₈D₃ ^(R6)M 90/10 7 5 1355 4-6 MD₄₈D₃ ^(R6)M 90/10 7 301549 7-9 MD₄₈D₃ ^(R6)M 90/10 9.5 5 4318 10-12 MD₄₈D₃ ^(R6)M 90/10 9.5 303803 13-15 MD₉₉D₃ ^(R6)M 90/10 7 5 1309 16-18 MD₉₉D₃ ^(R6)M 90/10 7 301860 19-21 MD₉₉D₃ ^(R6)M 90/10 9.5 5 2030 22-24 MD₉₉D₃ ^(R6)M 90/10 9.530 2391 25-27 MD₉₉D₃ ^(R6)M 90/10 9.5 30 2867 (buffered)² 28-30MD₄₅D_(3.5) ^(R7)M 90/10 7 5 951 31-33 MD₄₅D_(3.5) ^(R7)M 90/10 7 301349 34-36 MD₄₅D_(3.5) ^(R7)M 90/10 9.5 5 2619 37-39 MD₄₅D_(3.5) ^(R7)M90/10 9.5 30 3281 40-42 MD₄₅D_(3.5) ^(R7)M 90/10 9.5 30 9254 (buffered)²¹Reported values are the average of measurements taken on threedifferent hair switches treated under the same conditions. ²Aminomethylpropanol.

Control experiments on hair switches treated with a polysiloxane withoutthe linker and molecular hook (polydimethylsiloxane with a viscosity of350 centistokes) for 5 minutes showed an initial deposition level ofsilicon as 2050 parts per million by XRF. Measurements showed that after8 shampoos, no silicon remained on the hair. The data in Table 1 clearlyshow that the silicone polymers of the present invention which provideconditioning benefits, do adhere to the hair with unexpected durability.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing description should not be deemed to be alimitation on the scope of the invention. Accordingly, variousmodifications, adaptations, and alternatives may occur to one skilled inthe art without departing from the spirit and scope of the presentinvention.

What is claimed is:
 1. A method for making a silicone compositioncomprising at least one polysiloxane or silicone resin, at least onelinker, and at least one molecular hook, which method comprisescombining a linker, a molecular hook, and a polysiloxane or siliconeresin wherein the molecular hook comprises a heterocyclictrimethylpyrimidinium compound.
 2. The method of claim 1 wherein theheterocyclic trimethylpyrimidinium compound comprises the formula(VIII):

wherein Y represents a linker and Q⁻ represents a counterion.
 3. Themethod of claim 2, wherein Q⁻, is selected from the group consisting ofhalides, borates, phosphates, tosylates, mesylates, and triflates. 4.The method of claim 1 which comprises combining at least one linker witha polysiloxane or silicone resin and subsequently combining saidcombination with at least one molecular hook.
 5. The method of claim 1which comprises combining at least one linker with at least onemolecular hook and subsequently combining said combination with apolysiloxane or silicone resin.
 6. The method of claim 2 in which the atleast one linker is bound to a polysiloxane or silicone resin through asilicon, carbon, oxygen, nitrogen, or sulfur atom.
 7. The method ofclaim 6 in which the at least one linker is bound to a polysiloxane orsilicone resin through a silicon atom.
 8. The method of claim 1 in whichthe silicone composition comprises at least one compound of thefollowing formulas, (I), (II), (III), (IV), (V), (VI), or (VII):

 (R³⁷ ₃SiO_(1/2))_(a)[(Z—Y)R³⁸ ₂SiO_(1/2)]_(b)(SiO_(4/2))_(g)  (VII)where each R¹⁻³⁸ is independently at each occurrence a hydrogen atom,C₁₋₂₂ alkyl, C₁₋₂₂ alkoxy, C₂₋₂₂ alkenyl, C₆₋₁₄ aryl, C₆₋₂₂alkyl-substituted aryl, C₆₋₂₂ aralkyl, C₁₋₂₂ fluoroalkyl, C₁₋₂₂polyether, or C₁₋₂₂ amino alkyl; Z, Z¹⁻¹⁰, is independently at eachoccurrence, is a molecular hook; and Y, Y¹⁻¹⁰, independently at eachoccurrence, is a linker; wherein “m” in each formula has a value in arange between about 0 and about 13,000; “n” in each formula has a valuein a range between about 0 and about 13,000 with the proviso that informula (II) “n” is not 0; “m+n” in each formula has a value in a rangebetween about 1 and about 26,000; “q” has a value of at least one; “p+q”has a value of at least 3; “a” has a value greater than or equal to one;and “b” and “g” have a value of at least one.
 9. The method of claim 8in which the average number of Y-Z moieties on the polysiloxane orsilicone resin is between about 1 and about
 100. 10. The method of claim9 in which the average number of Y-Z moieties on the polysiloxane orsilicone resin is between about 1 and about
 10. 11. The method of claim8, wherein the silicone composition comprises at least one compound offormulas (I), (II), (III), (IV), or (V) wherein R¹⁻³³ is methyl; “m” ineach formula has a value in a range between about 20 and about 120; “n”in each formula has a value in a range between about 2 and about 10; and“m+n” in each formula has a value in a range between about 15 and about120.
 12. The method of claim 8, wherein the silicone compositioncomprises at least one compound of formula (VI), wherein “q” has a valueof at least one; “p+q” has a value in a range between about 3 and about6; and R³⁴⁻³⁶ is methyl.
 13. The method of claim 8, wherein the moietyZ—Y is prepared by a process which comprises combining a hook with alinker precursor comprising the linker and a leaving group.
 14. Themethod of claim 13, wherein the leaving group is selected from the groupconsisting of chloride, bromide, iodide, tosylate, mesylate, phosphate,and cyclic leaving groups containing at least one heteroatom.
 15. Themethod of claim 14, wherein the leaving group is iodide, chloride, orbromide.
 16. The method of claim 1, wherein the linker comprises aC₁-C₁₀₀ alkyl, aryl, or alkylaryl group optionally containing one ormore heteroatoms.
 17. The method in accordance with claim 16, whereinthe linker comprises at least one compound of the formula (IX), (X),(XI), (XII), (XIII), (XIV), or (XV):

where r is in a range between about 1 and about 10; s is in a rangebetween about 0 and about 100; t is in a range between about 0 and about100; u is in a range between about 1 and about 10; v is in a rangebetween about 1 and about 10; w is 1 or 2; x is 1 or 2; X is O, NOH,NOR, or NR; wherein R is independently at each occurrence hydrogen (H),C₁₋₂₂ alkyl, C₁₋₂₂ alkoxy, C₂₋₂₂ alkenyl, C₆₋₁₄ aryl, C₆₋₂₂alkyl-substituted aryl, or C₆₋₂₂ aralkyl where the C can beunsubstituted or substituted with heteroatoms such as oxygen (O),nitrogen (N), sulfur (S) or halogen; wherein R³⁹ is independently ateach occurrence hydrogen (H), C₁₋₂₂ alkyl, C₁₋₂₂ alkoxy, C₂₋₂₂ alkenyl,C₆₋₁₄ aryl, C₆₋₂₂ alkyl-substituted aryl, C₆₋₂₂ aralkyl, or fused ringsystem which may or may not be fused to the phenyl group where the C canbe unsubstituted or substituted with heteroatoms such as O, N, S orhalogen; A is O, NOH, NOR, NR or S; B is O, NOH, NOR, NR or S; and wherethe polysiloxane or the silicone resin is bound to the (CR₂)_(r)(Formula IX, X, XII, and XIII), (CR₂)_(v) (Formula XI and XIV), or(CR₂)_(w) (Formula XV).